Aerosol compositions

ABSTRACT

An aerosol composition of a phenolic polymeric material, a hydrocarbon propellant and a solvent is disclosed. The aerosol composition can be used to detect damaged sheets in pressuresensitive, mark-forming systems employing chromogenic materials and polymeric materials where one of the components is maintained in isolation as by encapsulation.

United States Patent Kay et al. Sept. 2, 1975 [54] AEROSOL COMPOSITIONS 2,968,644 I/ 1961 Norrhede 260/33.8 R

3,177,119 4/1965 Z0 bel 424/47 Inventors: Dame Kay; 9 Millers, 3,649,597 3/1972 Heiileyi 424/47 x both Of Dayton, 01110 3,672,935 6/1972 Miller et a1. 117/369 x [73] Assignee: NCR Corporation, Dayton, Ohio OTHER PUBLICATIONS [22] Filed; Apr. 2 974 T. S. Carswell, Phenoplasts, Interscience, New York Appl. No.: 460,409

Related US. Application Data Continuation of Ser. No. 312,405, Dec. 5, I972, abandoned, which is a division of Ser. No. 98,107, Dec. 14, 1970, abandoned.

US. Cl 427/; 427/ Int. Cl. B41M 5/00 Field of Search ll7/36.7, 36.9, 1.; 260/33.8 R, 33.8 U; 424/47 (1947) TP986 P4C3.

Primary Examiner-Thomas .1. Herbert, Jr. Attorney, Agent, or FirmRobert J. Shafer; E. Frank McKinney [57] ABSTRACT An aerosol composition of a phenolic polymeric material, a hydrocarbon propellant and a solvent is disclosed. The aerosol composition can be used to detect damaged sheets in pressure-sensitive, markforming systems employing chromogenic materials and poly meric materials where one of the components is maintained in isolation as by encapsulation.

2 Claims, No Drawings AEROSOL COMPOSITIONS This is a continuation of application Ser. No. 312,405, filed Dec. 5, 1972, now abandoned, which in turn is a divisional of application Ser. No. 98,107, filed Dec. 14, 1970, now abandoned.

This invention relates to an aerosol composition of a phenolic polymeric material.

Pressure-sensitive, markforming systems are known in the art. For example, see U.S. Pat. No. 3,672,935 issued June 27, 1972 on an application filed June 9, 1970 in the names of Robert E. Miller and Paul S. Phillips, .lr. These systems generally comprise a chromogenic (dye) material and polymeric material wherein at least one of the components is maintained in isolation from the other components, e.g., the dye can be isolated by encapsulation. In these pressure-sensitive, markforming systems, the support member, on which the components of the system are disposed, can comprise a single or multiple sheet assembly. In some instances, the coated-back sheet or sheets can be damaged in an undetectable manner. For example, in a single coatedback sheet, the color of the damaged sheet does not develop at all if damaged. In the multiple sheet assembly, the color does not develop until the coated-back sheet is placed in contact with the coated-front sheet and the printing and subsequent operations are complete. However, if the damage is severe enough, it may be clearly observable prior to printing. Naturally, such a method of detection of no detection at all is expensive as well as ineffective.

It now has been found that damged sheets can be detected by spraying the assembly with an aerosol composition comprising a phenolic polymeric material, a hydrocarbon propellant (or mixture of propellants) and a solvent (or mixture of solvents). The aerosol composition of this invention is unique in that it does not extract dye from undamaged capsules in the treated assembly. Note, this feature allows undamaged, but tested, sheets to be employed in the printing operation. Smudges, streaks, ghost images, lines and the like in assemblies which, are just slightly damaged now are as easily detected as more severely damaged sheets.

Accordingly, it is an object of this invention to provide an aerosol composition of a phenolic polymeric material.

Another object of this invention is to provide a process for producing a pressure-sensitive sheet.

Other objects, aspects and advantages of this invention will be apparent to one skilled in the art.

The aerosol compositions of this invention generally are employed to detect damage to assemblies of markforming components comprising a chromogenic material and a polymeric material reactive with the chromogenie material to produce a distinctive mark. The chromogenic materials in the unreacted state preferably are colorless, though light tones can be tolerated. Examples of these chromogenic materials are disclosed on columns 2 and 3 of the above-identified US Pat. No. 3,672,935. Normally, the chromogenic material is isolated from the other components by encapsulation.

The phenolic polymeric materials employed in these assemblies as well as in the aerosol compositions of this invention are certain phenol-aldehyde and phenolacetylene polymers, maleic acid'rosin resins, partially or wholly hydrolyzed styrene-maleic anhydride copolymers and ethylene-maleic anhydride copolymers, carboxy polymethylene (Carbopol 934), and wholly or partially hydrolyzed vinyl methyl ether maleic anhydride copolymer arespecified as typical of the reactive acidic polymeric materials. H:

Among the pherol-aldehyde polymers found useful are members of the type commonly referred to as novolacs, which are characterized by solubility in common organic solvents and which are, in the absence of crosslinking agents, permanently fusible. Another group of useful phenol polymeric materials are alkylphenolacetylene resins, likewise soluble in common organic solvents and possessing permanent fusibility in the absence of beingtreated by-cross-linking materials. Generally, the phenolic polymer material useful in practicing this invention is characterized by the presence of free hydroxyl groups and the absence of groups, such as methylol, which tend to promote infusibility or cross-linking of the polymer, and by their solubility in organic solvents and relative insolubility in aqueous media.

Resoles, if they are still soluble, may be used, though subject to changne in properties upon aging.

A laboratory method useful in the selectionof suitable phenolic resins is a determination of the infra-red absorpotion pattern. It has been found that phenolic resins showing an absorption in the 3200-3500 cm region (which is indicative of the free hydroxyl groups) and not having an absorption in the 1600-1700 cm'- region are suitable. The latter absorption region is indicative of the tie-sensitization of the hydroxyl groups and consequently maes such groups unavailable for reaction with the chromogenic materials.

The preparation of the phenolic-formaldehyde polymeric materials suitable for practicing this invention is described in Industrial and Engineering Chemistry," Volume 43, pages 134 to 141, January l, and'a particular polymer thereof is described in Example 1 of U.S. Pat. No. 2,052,093, issued to Herbert Hone] on Aug. 25, 1936, and the preparation of the phenolacetylene polymers is described in Industrial and Engineering Chemistry," Volume 41 pages 73 to 77, January 1949.

The preparation of the maleic anhydride copolymei's is described in the literature, such as, for example, one of the maleic anhydride vinyl cop'olymers, as disclosed in the publication Vinyl and Related Polymers, by Calvin E. Schildknecht, second printing, published Apr. 1959 by John Wiley & Sons, Incorporated. See pages 65 to 68 (styrene-maleic anhydride copolymer), 628 to 360 (vinyl methyl ee'thermaleic anhydride copolymer), and 530 to 531 (ethylene maleic anhydride copolymer). i

A wide variety of hydrocarbon propellants are employed in the aerosol compositions of this invention. The propellants can be halogenated or unhalogenated, preferably halogenated. Specific examples of propellants that can be employed in this invention are butane, isobutane, propane, Freon and the like and mixtures thereof. Preferably, Freon ll, Freon 12 or mixtures thereof are employed. Freon l l is trichloromonofluoromethanc and Freon 12 is dichlorodifluoromethane.

The solvents that are employed in the aerosol compositions of this invention are halogenated hydrocarbons such as trichloroethylene and perchloroethylene.

The aerosol composition of this invention is prepared by mixing the phenolic polymeric material in the solvent. The mixture then is introduced into a six ounce aerosol can with a one inch diameter opening. The air is purged from the can and capped with a valve. Then immediately thereafter the valve assembly is crimped into the aerosol can (neck). The valve used can be a commercially available one such as No. 041250 (Precision Valve Corp.) which has a 0.030 inch diameter orifice and a dip tubc extending well to the bottom of the aerosol can. The hydrocarbon propellant then is injected into the can through the valve. All ingredients then are mixed by gentle shaking. An activator is fitted on the valve stem, e.g., No. 041250 (Precision Valve Corp.) to complete the assembly. This aerosol unit will respond to finger-tip pressure applied at the top of the applicator to deliver the aerosol composition to any desired situs of use. Theconcentrations of the components by weight per cent are as follows:

General Usual Preferred Phenolic Polymeric Material 2 to 10 2 to 8 3 to 5 Hydrocarbon Propcllant 40 to 85 50 to 80 60 to 75 to 40 to 35 L5 to Solvent In a six ounce aerosol can, (a) 60 grams of 5 per cent Dures 26799 resin (Dures 26,799 is a para-tertiarybutyl phenolic resin) in trichloroethylene and 84 grams of Freon l l was added; (b) the air was purged from the can and capped with a Danvern valve; and (c) 72 cc. of Freon 12 were added through the valve Mixing was accomplished ,by gentle shaking. Another sample was prepared as above, except that grams of 5 per cent Durez 26799 resin in trichloroethylene and l 14 grams of Freon l l were employed in step (a).,

I A third sample was prepared as above, except that 15 grams of 5 per cent Durez 26799 resin in trichloroethylene and 129 grams of Freon 11 were employed in step (a). 7

EXAMPLE ll with an encapsulated chromogenic material. The chromogenic material being crystal violet lactone (CVL) as described in the previously identified US. Pat. No. 3,672,935.

On many of the samples, no blue CVL -resin color developed, indicating no damage. Some samples developed blue CVL resin color where the surface had been damaged, i.e., blue creases and crinkles were clearly evident. In every instance, other portions of the damaged sheets were sprayed with no development of color. These sprayed portions were then hit with a blunt instrument and blue CVL resin color developed, indicating that the spray does not extract dye from undamaged capsules. Still other sheets turned completely blue, indicating capsular damage caused by nip pressure.

The use of this invention, namely reactive phenolic resin spray, at the time of printing would enable the printer to immediately see capsular damage and make the necessary adjustments to the press collator and related paper handling equipment. The spray also could be used in coating, rewinding and collating processes of the manufacture of single, dual and multiple copy assemblies to determine damage.

What is claimed is:

1. A process for testing a pressure sensitive sheet to detect damaged capsules comprising:

a. establishing a support web or sheet material, to be tested, supporting on one surface a coating of a finely dispersed phase of a plurality of minute, pressure-rupturable capsules containing as an inner phase at least one substantially colorless or slightly colored chromogenic material dissolved in a solvent liquid vehicle; and

b. spraying said coating with an aerosol composition consisting essentially of at least one phenolic polymeric material, at least one hydrocarbon propellant, and at least one solvent of trichloroethylene or perchloroethylene, wherein the composition comprises 2 to l0 weight per cent of the phenolic material, 40 to weight per cent of the propellant resin. 

1. A PROCESS FOR TESTING A PRESSURE SENSITIVE SHEET TO DETECT DAMAGE CAPSULES COMPRISING: A. ESTABLISHING A SUPPORT WEB OR SHEET MATERIAL, O BE ESTED, SUPPORTING ON ONE SURFACE A COATING OF A FINELY DISPERSED PHASE OF A PLURALTTY OF MINUTE, PRESSURE-RUPTURABLE CAPSULES CONTAINING AS AN INNER PHASE AT LEAST ONE SUBSTANTIALLY COLORLESS OR SLIGHTLY COLORED CHROMOGENIC MATERIAL DISSOLVED IN A SOLVENT LIQUID VEHICLE, AND B. SPRAYING SAID COATING WITH AN AEROSOL COMPOSITION CONSISTING ESSENTIALLY OF AT LEAST ONE PHENOLIC POLYMERIC MATERIAL, AT LEAST ONE HYDROCARBON PROPELLANT, AND AT LEAST ONE SOLVENT OF TRICHLORETHYLENE OR PERCHLOROOETHYLENE, WHEREIN THE COMPOSITION COMPRISES 2 TO 10 WEIGHT PER CENT OF THE PHENOLIC MATERIAL, 40 TO 85 WEIGHT PER CENT OF THE PROPELLANT AND 10 TO 40 WEIGHT PER CENT OF THE SOLVENT WHEREBY CONTACT OF THE PHENOLIC POLYMERIC MATERIAL OF THE AEROSOL COMPOSITION WITH CHROMOGENIC MATERIAL OF THE CAPSULE CONTENTS RESULTS IN COLOR DEVELOPMENT AND INDICATES RUPTURE OF CAPSULES.
 2. A process according to claim 1 wherein the chromogenic material is crystal violet lactone (CVL) and the phenolic material is paratertiarybutyl phenolic resin. 